Image-receiving element for use in photographic silver salt diffusion transfer process

ABSTRACT

A method for producing an image-receiving element suitable for use in a silver salt diffusion transfer photographic process, wherein a water-soluble metal salt and either or both of a watersoluble sulfide and a water-soluble selenide are reacted with each other in an aqueous dispersion of silicon dioxide, the pH of which dispersion is not less than 8.0, to form the precipitate of the water-insoluble metal sulfide and/or selenide, the resulting reaction liquor being applied to a support and dried.

Ohkubo et al.

IMAGE-RECEIVING ELEMENT FOR USE IN PHOTOGRAPI-IIC SILVER SALT DIFFUSION TRANSFER PROCESS Inventors: Kinji Ohkubo; Kazunobu Kato, both of Kanagawa, Japan Assignee: Fuji Photo Film Co., Ltd.,

Kanagawa, Japan Filed: Sept. 16, 1971 Appl. No.: 181,209

Foreign Application Priority Data Sept. 28, 1970 Japan 45-84537 US. Cl. 96/76 R, 96/29 R Int. Cl. G03c l/48 Field of Search 96/76, 29; 117/367; 423/335 References Cited UNITED STATES PATENTS 12/1954 Land 96/29 R 1 Feb. 11, 1975 2,698,245 12/1954 Land 96/29 2,757,073 7/1956 Drexel 23/182 2,823,122 2/1958 Land 96/29 3,060,022 10/1962 Duerr 96/29 3,345,168 10/1967 Wagner et al. 96/29 3,445,228 5/1969 Beavers et al. 96/29 Primary ExaminerDavid Klein Assistant Examiner-John L. Goodrow Attorney, Agent, or Firm-Sughrue. Rothwell, Mion, Zinn & Macpeak [57] ABSTRACT A method for producing an image-receiving element suitable for use in a silver salt diffusion transfer photographic process, wherein a water-soluble metal salt and either or both of a water-soluble sulfide and a water-soluble selenide are reacted with each other in an aqueous dispersion of silicon dioxide, the pH of which dispersion is not less than 8.0, to form the precipitate of the water-insoluble metal sulfide and/or selenide, the resulting reaction liquor being applied to a support and dried.

9 Claims, No Drawings IMAGE-RECEIVING ELEMENT FOR USE IN PHOTOGRAPI-IIC SILVER SALT DIFFUSION TRANSFER PROCESS BACKGROUND OF THE INVENTION 1. Field of the Invention This invention relates to an image-receiving element for use in a photographic silver salt diffusion transfer process.

2. Description of the Prior Art In the hitherto known diffusion transfer photographic processes wherein there is employed a light-sensitive photographic element comprising a support having coated thereon a dispersion of fine particles of a light therein the silver precipitating nuclei of particularly high activity is very useful as a high speed silver salt diffusion transfer photographic element for the purpose of photographing. US. Pat. No. 2,698,237 teaches the use 5 of particularly highly active silver precipitating nuclei, the method for the preparation of which comprises admixing both a water-soluble metal salt and a water soluble sulfide in an aqueous dispersion containing in particular, particulate silicon dioxide to form the precipitate of the waterinsoluble metal sulfide, which serves as the silver precipitating nuclei. When the aqueous dispersion of silicon dioxide containing therein the silver precipitating nuclei is applied onto a support sheet the resulting image-receiving element yields, when subsensitive silver salt, (such as a silver halide) in a hydrojected to a silver salt diffusion transfer process, a posi' philic binder such as gelatin, the light-sensitive layer tive print, carrying images of excellent quality. thereof was ex osed to Ii ht ima ewise and then contacted with a? processii ig con position containing SUMMARY OF THE INVENTION therein, a developing ge t o effeei v l p of The present invention relates to an improved method the light-sensitive silver salt. At this point, the Xp05d for producing ilver precipitating nuclei in a ilicon silver halide in the light-sensitive layer is thereby reid di d more ti l rl to a meth d f r duced p i0 fOim metaiiic Siivfiiproducing an image-receiving element suitable for use cohcuriehiiy therewith 0i Subsequently thereto ihe in a silver salt diffusion transfer photographic process light-sensitive maieriai is processed with a Waieiwherein a water-soluble metal salt and at least one of Soluble complex forming agent, whereby the either a water-soluble sulfide or a water-soluble selewater-soluble silver complex is formed by reaction of id i reacted i h h other i an aqueous di t n xp (undeveloped) Silver halide with Said sion of silicon dioxide having a pH of not less than 8.0 agent The", Concurrently therewith, an g to form a precipitate of the water-insoluble metal sulrficeivihg element having a iayer image-receiving fide or metal selenide, the resulting reaction liquor layer) containing therein, a substance dispersed in a hy- 0 b i appligd to a Support d d i d, drophilic binder, which serves as a catalyst for reduci h b f d that, h h i i i l tion of the above-mentioned water-soluble silver commeht d d b h h d f hi invention i plex (the substance being therefore the silver precipii d i diffusion transfer processes, a positive print tating nuclei, or so called physical development nuclei) f exceptional quality can be obtained h i is brought into ihiimaie Contact with the afoi'emenreceiving element thus produced gives a positive print tioned light-sensitive negative layer. The silver complex f increased maximum density, which is glossy and formed in the light-sensitive layer is, at least in part, moderate grey i color DETAILED DESCRIPTION transferred from the light-sensitive negative layer to the OF THE iNVENTiQN image-receiving l y r. Where it is i'fiduced to silver Silicon dioxide is often called silicic acid anhydride under ihfi effect of the Physicai deVeiQpmem nuclei 40 and is itselfan acidic substance.Therefore,it produces, Contained therein thereby forming the desired images when dispersed in water, silicic acid owing to partial having a Paiieih corresponding to the oiigihai hghihydration, the pKa and pKa of which being 9.8 and sensitive negative layer. 12.16 at 30C, respectively.

As the silver precipitating nuclei, which may be used It is desirable that the silicon dioxide be in the form in the aforementioned silver salt diffusion transfer phoof particles as fine as possible. Examples of the silicon tographic process, there may be mentioned, for examdioxide suitable for the purpose of this invention and pie, metal sulfides, which are normally water-insoluble, commercially available are listed in the following table. metal selenides or colloidal heavy or noble metals. In In the last column of the table are shown pH values of forming the image-receiving element, these silver prethe aqueous solutions of the respective silicon dioxide. cipitating nuclei are dispersed in a polymer such as These values are all reported ones, disclosed by each galatin or polyvinyl alcohol through which an alkaline manufacturer. As previously stated, an aqueous dispersolution is able to permeate and the dispersion thus obsion of silicon dioxide is itself acidic. tained applied onto a suitable support, such as paper, However, in order to prevent gelation, silicon dioxide film or a metal plate. is often commercially available in the form of an alka- In addition, the image-receiving element containing line aqueous dispersion.

Maker Trade Name Form pH Monsanto Chemical Co. Santoccl 54 4% aqueous dispersion 3.8 do. do. C do. do. 3.8 do. do. L do. do. 4.0 do. do. 62 do. do. 3.8 do. do. FRC do. do. 3.8 Nippon Acrosil K.K. Acrosil I30 4% aqueous dispersion 3.6-4.3 do. do. 200 do. do. 3.6-4.3 do. do. 300 do. do. 3.64.3 do. do. (i do. do. 3.0-4.3 do. do. 380 do. do. 311-4.] do. do. MOXXU do. do. 3.6-4.2 do. do. (OKX-i do. do. iii-4.0 do. do. MOK I 71) do. do. 3.b-4.2

Maker Trade Name Form pH W.R. Grace Co. Davison Chemical Division Syloid 308 57: aqueous dispersion 2.4 do. do. 404 do do. 7.0 do. do. AL-l do do. 3.8 do. do. 65 do. dov 3.8 do. do. 978 do do. 2.4 do. do. 161 do. do. 7.0 do. do. 162 do do. 7.0 do. do. 244 do do. 7.0 do. do. 75 do. do. 7.0 E.l. duPont de Nemours & Co. Ludox HS-4O 40.1% aqueous dispersion 9.6 do. do. HS-3O 30.1 do. 9.8 do. do. LS 30.1% do. 8.3 do. do. AS 30.1% do. 9.4 do. do. AM 30 do. 9.1 do. do, SM 30 do. 9.9 Nissan Chemical Industries,

Ltd. Snowtex 20-21% aqueous dispersion 9.510.() do. do. 30 30-31% do. 9.5-10.5 do. do. 40 40-41% do. 9.5-10.5 do. do. C 20-21% do. 8.5-9.0 do. do. N do. do. 8.0-9.5 do. do. 0 do. do. 3.0-4.0

These aqueous dispersions of silicon dioxide are colloidal and most of the pH values thereof are indicative of an acid to neutral pH, although some dispersions exhibit an alkaline pH, for example, Snowtex 20, Snowtex 30, Snowtex 40, Snowtex C, Snowtex N and Ludox homologues.

In an embodiment of the present invention, to an aqueous dispersion of silicon dioxide which exhibits an acidic to neutral pH, as for example Santocel 54, Santocel C, Snowtex O or Aerosil 300, is added an alkali agent to maintain the pH of the aqueous dispersion alkaline, in which dispersion silver precipitating nuclei are formed. The resulting aqueous dispersion of silicon dioxide containing therein the silver precipitating nuclei obtained is then applied onto a suitable support and dried. The image-receiving element thus obtained yields, when applied to a silver salt diffusion transfer process, a positive print carrying images of good quality. For this purpose, there may be employed any alkali agent, examples of which include inorganic alkali agents, such as sodium hydroxide, potassium hydroxide, lithium hydroxide or ammonia, or organic bases, such as ethanol amine or the like.

As the support for the image-receiving element of this invention, there may be employed any suitable support, for example, films (of cellulosic derivatives, such as regenerated cellulose, cellulose diacetate, cellulose triacetate or ethyl cellulose, polyethylene, polypropylene, polyester or the like materials), papers, baryta coated papers, polystyrene papers, polyethylenelaminated papers or the like.

The particularly suitable silver precipitating nuclei are metal sulfides and metal selenides, of which, of

a 6% aqueous solution of saponin 5.

course, selenium sulfide, polysulfides and polyselenides are included. Examples of those sulfides or selenides include the sulfides orselenides of zinc, cadmium, lea'd, iron, nickel, cobalt, and tin. These are obtained by admixing a water-soluble metal salt, such as acetate, nitrate, borate, chloride, sulfate, hydroxide, formate or citrate with a water-soluble sulfide, such as sodium sulfide.

Furthermore, the preferred silver precipitating nuclei include heavy metals, such as silver, gold, platinum or mercury, which are added to the silicon dioxide dispersion as colloidal particles, or added to the silicon dioxide dispersion as their water-soluble metal salts, in the latter case, by reduction to form the colloidal metal nuclei.

A better understanding of the present invention will be further gained by the following examples, which are merely intended to be illustrative and not limitative of the present invention.

EXAMPLE 1 lnto a 250 c.c. of a 5% aqueous dispersion of Santocel C (pH 3.8) are added, with stirring, the following aqueous solutions in order: 1,

a 2% aqueous solution of lead acetate (trihydratc) l a 3% aqueous solution of cadmium acetate (dihydrate) 2. a 5% aqueous solution of zinc nitrate (hexahydrate) 5 a 12% aqueous solution of sodium sulfide (nonahydrate) 1 an The resulting dispersion is then applied to a support at a coverage of 20 c.c./m. and dried. As the support, there is employed a polyethylene-laminated paper hydrophilized by corona discharge-treatment of its surface.

EXAMPLE 2 The pH of a 5% aqueous dispersion of Aerosil 300 (initial pH 3.6, 250 c.c.) is raised to a pH of 9.5 with the addition of l N sodium hydroxide, into which dispersion, after sufficient stirring, the following aqueous solutions are added, with stirring, in order:

a 2% aqueous solution of lead acetate (trihydrate) l.5 c.t a 3% aqueous solution of cadmium acetate (dihydrate) 2.3 cc a 5% aqueous solution of zinc nitrate (hexahydrate) 5.0 c.c a 3% aqueous solution of sodium sulfide (nonahydrate) 1.0 cc and a 6% aqueous solution of saponin 5.0 c.c

The resulting composition was then applied onto a support at a coverage of 20 c.c./m. and dried.

As the support, there is employed a polyethylene laminated paper hydrophilized by applying coronadischarge treatment to the surface thereof.

EXAMPLE 3 The pH of a 5% aqueous dispersion of Santocel 54 (initial pH 3.8, 250 c.c.) is raised to a pH of 10.0 by the addition of l N sodium hydroxide, and then sufficiently stirred, after which, in the same manner as in Example 2, the aqueous solutions of the metal salts and the aque' ous solution of sodium sulfide described in Example 2 are successively added. The resulting composition was applied onto a polyethylene-laminated paper hydrophilized by the surface corona-discharge treatment, at a coverage of 20 c.c./m

EXAMPLE 4 The pH of a 5% aqueous dispersion of Snowtex (pH 3.8, 250 c.c.) is raised to a pH of 9.8 by the addition of sodium hydroxide (l N) and then sufficiently stirred, after which, in the same manner as in Example 2, the aqueous solutions of the metal salts and the aqueous solution of sodium sulfide described in Example 2 are successively added. The resulting composition is applied onto a polyethylene-laminated paper hydrophilized by the surface corona-discharge treatment, at a coverage of 20 c.c./m

EXAMPLE Into 250 c.c. ofa 5% aqueous dispersion of Snowtex 30 (pH 9.5) are added the aqueous solutions of the metal salts and the aqueous solution of sodium sulfide described in Example 2, the resulting composition being applied onto a polyethylene-laminated paper bydrophilized by the surface corona-discharge treatment at a coverage of c.c./m

The image-receiving element obtained in each of the abovementioned examples is then brought into intimate contact with an imagewisely exposed negative element in a manner such that the image-receiving layer may be surface contacted with the emulsion layer surface, between which surfaces is spread a diffusion transfer processing composition in a viscous condition. As the negative element, there may be employed those used as high speed photographic materials in which a silver iodobromide emulsion is applied onto a suitable Here we have employed the following processing composition:

Water 1,860 g. Sodium salt of carboxymethyl cellulose ll7 g. Sodium sulfite (anhydrous) 78 g. Sodium hydroxide 74.6 g. Sodium thiosulfate (crystalline) 14.5 g. Citric acid 38.5 g. Hydroquinone 52 g.

The negative element is kept in contact with the image-receiving element for 15 seconds and subsequently, the former is separated from the latter. The positive print obtained on the image-receiving element was measured for its maximum transferred density (expressed in terms of reflection density) to obtain, 0.70 for the image-receiving element obtained in Example l, 1.15 for the image-receiving element obtained in Examples 2, 3 and 4, and 1.40 for the image-receiving element obtained in Example 5, respectively. Furthermore, with the image-receiving elements obtained in Examples 2, 3 and 4 there were obtained glossy beautiful positive prints.

The reason why the image-receiving element con taining the silver precipitating nuclei formed in the alkaline silicon dioxide dispersion can provide the positive print of excellent quality is not only due to the fact that the alkaline atmosphere in the image-receiving element accelerates the developing reaction, but that the silver-precipitating nuclei themselves are different in their activity in their alkaline and neutral to acidic conditions. The silver precipitating nuclei are supposed to be deposited on the surfaceof the colloidal silicon dioxide, the electric conditions of the surface of the silicon dioxide particles being quite different under alkaline and neutral to acidic conditions. Consequently, it is quite probable that the deposition of the silver precipitating nuclei differs in its mechanism and the resulting silver precipitating nuclei also differ in their respective condition. Furthermore, in producing the precipitate of the aforementioned metal sulfides, the pH dependence of the precipitate formation entirely differs among the specific metal ions.

Accordingly, when an aqueous sodium sulfide solution is added to an aqueous solution of a mixture of several metal salts to form the precipitate of the mixed crystals of the metal sulfides, the composition of the resulting mixed crystals varies with the pH of the specific system. Furthermore, it is quite probable that these compositions are rich in activity regarding the silver precipitating nuclei, whereas other compositions are poor in such activity.

It is believed that the achievement of excellent properties in the silver precipitating nuclei prepared in the alkaline silicon dioxide dispersion results from at least two of the above-mentioned reasons. Such technique has not yet been known and thus is novel.

Although the present invention has been described in considerable detail with reference to certain preferred embodiments thereof, it will be understood that various changes and modifications can be effected without departing from the spirit and scope of the invention as described hereinabove and defined in the appended claims.

What we claim is:

1. A method for producing an image-receiving element suitable for use in a silverdiffusion transfer photographic process comprising:

providing an aqueousdispers'ion of silicon dioxide having an acidic to neutral pH; adding to said aqueous dispersion an alkali agent to adjust the pH to not less than 8.0; thereafter reacting in said aqueous dispersion of silicon dioxide a water-soluble heavy metal salt with either or both a water-soluble metal sulfide and a water-soluble metal selenide to form a precipitate of a water-insoluble metal sulfide and/or selenide;-

applying the resulting reaction liquor onto a support; and drying. 2. The method of claim 1, wherein said metal sulfide is a member selected from the group consisting of sulfide, selenium sulfide and a polysulfide.

3. The method of claim 1, wherein said metal selenide is a member selected from the group consisting of a selenide and a polyselenide.

. ganic alkali agents and organic bases.

8. The method of claim 1, wherein said silicon dioxide is in the form of water glass.

9. The method of claim 1, wherein said heavy metal is a member selected from the group consisting of silver, gold, platinum, and mercury. 

1. A METHOD FOR PRODUCING AN IMGAE-RECEIVING ELEMENT SUITABLE FOR USE IN A SILVER DIFFUSION TRANSFER PHOTOGRAPHIC PROCESS COMPRISING: PROVIDING AN AQUEOUS DISPERSION OF SILICON DIOXIDE HAVING AN ACIDIC TO NEUTRAL PH; ADDING TO SAID AQUEOUS DISPERSION AN ALKALI AGENT TO ADJACENT THE PH TO NOT LESS THAN 8.0; THEREAFTER REACTING IN SAID AQUEOUS DISPERSION OF SILICONDIOXIDE A WATER-SOLUBLE HEAVY METAL SALT WITH EITHER OR BOTH A WATER-SOLUBLE METAL SULFIDE AND A WATER-SOLUBLE METAL SELENIDE TO FORM A PRECIPITATE OF A WATER-INSOLUBLE METAL SULFIDE AND/OR SELENIDE; APPLYING THE RESULTING REACTION LIQUOR ONTO A SUPPORT; AND DRYING.
 2. The method of claim 1, wherein said metal sulfidE is a member selected from the group consisting of sulfide, selenium sulfide and a polysulfide.
 3. The method of claim 1, wherein said metal selenide is a member selected from the group consisting of a selenide and a polyselenide.
 4. The method of claim 1, wherein said heavy metal is a member selected from the group consisting of zinc, cadmium, lead, iron, nickel, cobalt and tin.
 5. The method of claim 1, wherein the anion of said watersoluble heavy metal salt is a member selected from the group consisting of acetate, nitrate, borate, chloride, sulfate, hydroxide, formate and citrate of said metal.
 6. The method of claim 1, wherein said water-soluble sulfide is sodium sulfide.
 7. The method of claim 1, wherein said alkali agent is a member selected from the group consisting of inorganic alkali agents and organic bases.
 8. The method of claim 1, wherein said silicon dioxide is in the form of water glass.
 9. The method of claim 1, wherein said heavy metal is a member selected from the group consisting of silver, gold, platinum, and mercury. 